Polyesters and polyamides bearing pendant quaternary ammonium groups



United States Patent 3,533,998 POLYESTERS AND POLYAMIDES BEARING PENDANT QUATERNARY AMMONIUIVI GROUPS Seymour Yolles, Fairfax, Wilmington, DeL, assignor to E. I. du Pout de Nemours and Company, Wilmington,

Del., a corporation of Delaware No Drawing. Filed June 8, 1967, Ser. No. 644,501

Int. Cl. C08g 17/14, 20/30, 20/32 US. Cl. 260-65 4 Claims 10 ABSTRACT OF THE DISCLOSURE- (A) Polyesters and polyamides bearing pendant quaternary ammonium groups, useful as antistatic agents and as initiators for the preparation of (B) novel polymers derived from 2,2-substituted hydroxy propionic acids and 2,2-substituted propiolactones, also useful as antistatic agents.

The polyesters and polyamides have recurring units rep- I resented by the structure X is alkyl or benzyl,

Y is alkylene, alkylene ether, arylene ether, polyalkylene ether, phenylene, arylene or cycloalkylene, and

D is oxygen or v The polymers derived from 2,2-subst1tuted hydroxy pro'pionic acids and 2,2-substituted propiolactones hav recurring units represented by the structures 3,533,998 Ice Patented Get. 13, 1970 and where R, X, D and Y are as above, R1 iS Z is hydrogen or alkyl of 1-10 carbon atoms, and m is 10-5000.

I SUMMARY OF THE INVENTION This invention relates to polyesters and polyamides bearing pendant quaternary ammonium radicals. It is more particularly directed to polyesters and polyamides having'recurring units represented by the structures iaiaiiwl fifo-mxi J R is a' tetravalent organic radical having at lea'st' 6 car bon atoms,

Hie-ori R1 is l- Ha-CHP where X is a linear or branched alkyl radical of 1 through 18 carbon atoms or benzyl, (usually only'one of X is benzyl), I

Dis oxygen or and Y is phenylene, cycloalkylene of up to 20- carbon-atoms,

a' linear or branched The invention is also directed to polymers derived from 2,2-substituted hydroxypropionic acids and 2,2- substituted propiolactones. These polymers have recurring units represented by the structures R, R D, X and Y are defined as in Formula 1,

Z is hydrogen or an alkyl radical of 1-10 carbon atoms,

and

m is -5000.

In Formulae 1 and 2, the R group, because it bears four carboxyl groups, can accept the various moieties attached to it in configurations other than that shown. These moieties may be in any position relative to each other, e.g., 1,2; 1,3; or 1,4 when R is phenyl.

Illustrative of the R groups in Formulae 1 and 2 are I ll The polyesters and polyamides of Formula 1 can be made by reacting a dianhydride with an alkanediol, a diamine, an alkyl ether glycol or a polyether glycol according to the general and illustrative equation The carboxyl groups in the resulting polyester can then be neutralized with a tetraalkyl ammoniumor trialkylbenzylammom'um hydroxide.

Illustrative of the dianhydrides which can be used are trimellitic anhydride pyromellitic dianhydride 2,3,6,7-naphthalene tetracarboxylic dianhydride l,2,5,6-naphthalene tetracarboxylic dianhydride 3,3',4,4'-diphenyl tetracarboxylic dianhydride 2,2',3,3'-diphenyl tetracarboxylic dianhydride 2,2-bis( 3,4-dicarboxyphenyl) propane dianhydride 2,2-bis(2,3-dicarboxyphenyl) propane dianhydride l, l-bis (2,3-dicarboxyphenyl) ethane dianhydride 1,l-bis(3,4-dicarboxyphenyl) ethane dianhydride bis(2,3-dicarboxyphenyl) methane dianhydride bis(3,4-dicarboxyphenyl) methane dianhydride (benzenel,2,3,4-tetracanboxylic dianhydride) bis(3,4-dicarboxyphenyl) sulfone dianhydride bis(3,4-dicarboxyphenyl) ether dianhydride pyra2ine-2,3,5,6-tetracarboxy1ic dianhydride thiophene-Z,3,4,5-tetracarboxylic dianhydride and 3,4,3',4-benzophenone tetracarboxylic dianhydride.

Illustrative of the diamines which can be used are hexamethylene diamine phenylene diamine 4,4'-diaminodiphenyl ether 4,4-methylene-bis-(cyclohexylarnine) and 2,3,5,6-tetrach1oro p-Xylene-a,a'-diamine.

Illustrative of the alkanediols, alkyl ether glycols and polyether glycols which can be used are ethylene glycol 1,3-propanediol 1,4-butanediol 1,6-hexanediol trans,trans-1,4-cyclohexanediol 2,2,4,4-tetramethyl-1,3-cyclobutanediol polyethylene glycol (molecular weight 1064000) polypropoylene glycol (molecular weight l344000) polytetramethylene glycol (molecular weight 162-5000).

The reaction shown in Equation 3 is run by slurrying equimolar amounts of an anhydride and an alkanediol, diamine, alkyl ether glycol or polyester glycol in an organic liquid such as xylene, methylethyl ketone, cyclohexanone or tetrahydrofuran. The reaction proceeds quickest if the dianhydride reactant is soluble in the organic liquid; tetrahydrofuran is preferred for this reason.

This slurry is stirred and heated for about two hours at reflux temperature. The progress of the reaction can be followed by periodically determining the acid number of the reaction mass. When the theoretical acid number is reached, the reaction is complete. The molecular weight of the product can be controlled by introducing an excess of either reactant, which acts as a chain stopper.

The resulting polyester is a colorless to light yellow viscous liquid or gum which can have a molecular weight ranging from about 500 into the hundreds of thousands. In substantially pure form, the product is a mixture of polymers having different molecular weights.

This polyester precursor is then treated with a quaternary ammonium hydroxide by dissolving or dispersing it in water or an alcohol such as methanol and then titrating this with a solution of quaternary ammonium hydroxide in alcohol or water to an end point of pH 9-10. The polyester of Formula 1 can be recovered from this by evaporating the liquid. The product is a substantially pure colorless to light yellow semi-solid. Its molecular weight is about the same as the polyester precursor.

The polyesters and polyamides of Formula 1 are useful as initiators for the polymerization of 2,2-substituted hydroxypropionic acids and 2,2-substituted propiolactones to give polymers of Formula 2. The polymerization and can be carried out by first preparing a 1-2%, (by weight) solution of a Formula 1 polyester in hexane or benzene and then dripping in the acid or lactone monomer, with 6 especially aluminum flake and titanium dioxide. Such metallic pigments, when used in outdoor paints, sometimes cause staining of the finish when exposed portions of the pigment react with acids or bases in the atmosphere. A polymeric coating, easily provided by the method just described, shields the pigments from exposure to the atmosphere and so provides stain-free finishes.

The polymers of Formulae 1 and 2 are also useful as antistatic agents. Fibers and fabrics which are prone to develop high electrostatic charges, especially when there is little moisture in the air, will retain little or no charge if they are treated with a polymer of Formula 1 or 2. The fabrics or fibers can be treated by simply immersing them in a 0.5% to 5% solution of a polymer in a solvent such as Water or methanol, and then drying them.

Preferred for their initiating ability in the solvent-, fluidized bedor the Vapor-phase polymerization, and for their antistatic properties, are polymers having recurring units represented by the structures stirring. A polymer of Formula 2 precipitates.

The polyesters and polyamides of Formula 1 are especially useful as initiators for polymerizing these acid or lactone monomers from the vapor phase, an efiicient technique for coating articles With a Formula 2 polymer. To do this, one simply impregnates or coats the object to be coated with a 0.5% to about 20%, (by weight) solution of the polyester initiator in water or tetrahydrofuran, allows it to dry and then exposes it to monomer vapor at a temperature of from to 100 C. for from to 300 minutes. The Formula 2 polymer forms in situ, coating the object with a smooth and continuous film.

This vapor phase technique can also be used to give various types of fibers smooth continuous coatings of Formula 2 polymers. Paper made from such coated cellulose fibers, when hot pressed, becomes bonded at (CHaCH2CH2CH points of fiber intersection to give a rigid inert sheet useful as battery separators, siding, and the like. Asbestos fibers coated in this way can be similarly pressed into ceramic-like articles, and wool becomes shrinkproof and dimensionally stable. Hair treated in this fashion retains a preformed curl.

The polyesters and polyamides of Formula 1 are also useful as initiators for the solventor fludized bed deposition of Formula 2 polymers. The initiator is applied as before to the object to be coated; this object is then suspended in an inert liquid such as hexane or benzene, or in a fluidized bed. Acid or lactone monomer liquid or vapor is then passed in. The polymerization proceeds as before to give a coating of the Formula 2 polymer.

This solventor fluidized bed technique is particularly useful for coating metal and metal oxide pigments,

A solution of 10.9 parts of sublimed recrystallized pyromellitic dianhydride in 50 parts of anhydrous tetrahydrofuran :was prepared. This solution was then added to a solution of 30 parts of dried Carbowax 600 1 in parts of tetrahydrofuran.

The resulting solution was heated to 68 C. and stirred for nine hours under nitrogen. The tetrahydrofuran was then distilled off, leaving behind 43 parts of light-yellow residue.

This residue was dissolved in parts of methanol and titrated with a 25% solution of tetrabutyl ammonium hydroxide in methanol to an end point of pH 9.1. The methanol was then removed at reduced pressure, leaving behind 67 parts of a yellow semi-solid polyester having recurring units represented by the structure A solution of 32.2 parts of benzophenone tetracarboxylic dianhydride in 50 parts of anhydrous tetrahydrofuran was prepared. This solution was then added to 60 parts of dried Carbowax 600 dissolved in 115 parts of tetrahydrofuran.

The resulting solution was heated to 68 C. and stirred for nine hours under nitrogen. The tetrahydrofuran was then distilled off, leaving behind a light-yellow residue.

This residue was dissolved in 150 parts of methanol and titrated with a 25% solution of tetrabutyl ammonium hydroxide in methanol to an end point of pH 9.5. The methanol was then removed at reduced pressure, leaving A polyethylene ether glycol having a molecular weight of about 600, sold by Union Carbide Co.

7 behind a polyester having recurring units represented by at 60 C. for 30 minutes. The fabric showed a weight inthe structure crease of about 2.5%.

l' u it u l --OC- --C C--O CHgCH2-O'CH2CHz 5.3 (CHaOH2CH2CHz N+ -0 0-0- N' GH2CH2OH2CH3) Example 3 A static charge placed on this fabric dissipated much more rapidly than did a charge placed on an untreated Th E l t 21.8

e procedure of Xamp e 1 was repea ed usmg control. ThlS antlstatic property was largely lost on launparts of pyromellitic dianhydride instead of 10.9 parts and using 95 parts of polytetramethylene ether glycol (molecderingular weight about 950 in place f the Carbowax 0 The fabric was then placed 1n a desiccator containing The resulting product was titrated to an end point of plvalolactone. and a vacuum of of mercury was pH 9.5 with tetrabutyl amomnium hydroxide to give a 15 drdwll- After one hour of exposure, the Vacuum was light-yellow semi-solid polyester having recurring units leased and the fabric removed and heated at 60 C. for represented by the structure 10 minutes. The fabric showed a weight gain of 2.3%.

0 F H H r l ---OC CO(GH2OH2CH2CH2O--CH2OH2CH2CH$7- 7-5 (CHzCHzCHzCHz N' *O-C CO N+ CH2OHzOHzCH O 0 Example 4 A static charge placed on this fabric also dissipated much more rapidly than did a charge placed on an untreated control. This antistatic property was left largely unaffected by laundering.

Fifty parts of dried crysotile asbestos were blended in an Osterizer with 800 parts of a 5% aqueous solution of the polyester of Example 1. The asbestos fibers were then removed from the slurry by filtration, washed twice with Example 7 water and then sucked dry on a filter funnel. The fibers were then dried for 24 hours at 70 C. The weight gain One hundred parts of Alcoa grade 216 aluminum flake was about 1%. were washed in acetone, dried and then slurried in 200 These dried fibers were then flutfed in an Osterizer, parts of benzene. This slurry was then mixed with a soluplaced in an open dish and the dish placed in a desiccator tion of 200 parts of a 9% benzene solution of the polycontaining pivalolactone. The pressure was then reduced ester of Example 3. The aluminum flake was then filto about 20 mm. tered from the liquid and dried.

After 66 hours, the fibers were removed from the desic- The flake was resuspended in 400 parts of benzene, cator and heated at 70 C. for about 1 hour. The product and 20 parts of pivalolactone were slowly dripped in, showed a weight gain of about 1.4%. with stirring, over a two-hour period. The flake was then Electronmicrographs of the fibers showed they were filtered from the solution. encapsulated with a polymer. This polymer had recurring The resulting paste was incorporated into an automounits of the structure tive lacquer. This lacquer, applied to a metal panel and Test bars 0.108 inch thick, made by compression molddried, gave a finish having improved resistance to staining this product at 225 C., showed the following charing by acids and bases. i l i b ak4548 Examp 1e 8 g gg g g Ninety parts of a long fiber kraft wood pulp slurry Modulus-402,843 p.s.i. containing 6.8 parts of wood were washed with 500 parts Exam 1e 5 of a 4% aqueous solution of the polyester of Example p 1. The fibers were then removed from the liquid by fil- Three parts of Orlon Acrylic F1ber, dried to connation, dried and fl ff d Stem Weight, were Soaked in a 5% aqueous Solution of These fibers were then placed in a desiccator containthe Polyester Example fibers were Separated ing pivalolactone, which was then evacuated to 20 mm. r t S01I1t1011 y filtrfltlon and then dned- They of pressure. The fibers were allowed to remain in this showed an 1 Increase In Welghtatmosphere for 48 hours and were then removed and These fibers were then exposed to plvalolactone vapor dried m a desiccator at a pressure of 20 mm. After 30 mm- Paper hand Sheets 50 l Per ream) re prepared e the filzers were removed from the deslccator and from these polymer-coated fibers by standard paper makdl'led at ing techniques. The sheets had good wet strength but polymer coated fibers more reslstailt to rather poor dry strength. Pressing several sheets together POOhlOrlte bleach and to Yellowmg on laundenng than at 423 F. and 32,000 lbs. ram pressure for 30 seconds the Same fibers left untreated' 70 gave a Well-bonded laminate which was impervious to Example 6 water and did not weaken or disintegrate when soaked in A 4 inch by 4 inch square of Dacron Polyester Fidil t h d m i id for 2 t 3 d ber taffeta was soaked for ten minutes in a 5% aqueous solution of the Example 1 polyester. The taffeta was then wrung out, air dried for 20 minutes and then dried Hair on a plastic curler was treated with a 1% solu- Example 9 tion of the polyester of Example 1, was allowed to dry overnight, and was then exposed to pivalolactone vapors in a vacuum desiccator. After 30 minutes, the hair showed a 0.8% weight gain. When removed from the curler, the hair retained the impressed wave. In water, this curl relaxed somewhat but retained about 50% of the original wave.

Example A sample of virgin wool, dried to constant weight, was washed with a 4% aqueous solution of the polyester of Example 1. The wool was then dried in a vacuum oven overnight at 55, and exposed to pivalolactone monomer in a desiccator at a pressure of mm. of mercury.

The tactile properties of the wool thus treated were indistinguishable from the untreated wool, and in addition was shrink-proof and had dimensional stability.

I claim:

1. A polymer consisting essentially of the recurring unit where R is and Y is phenylene, cycloalkylene of up to 20 carbon atoms,

2. A polymer according to Formula A in claim 1, wherein R is D is O, Y is CHzCHzOCH2CHz- 8;

and X is CH CH CH CH 3. A polymer according to Formula A in claim 1 wherein R is D is O, Y is {CHzCHz-O-C'HzCH29-g;

and

4. A method for reducing the receptivity of a fiber to an electrostatic charge, said method comprising coating or impregnating said fiber with a polymer according to claim 1.

References Cited UNITED STATES PATENTS 3,053,783 9/1962 Broadhead et al. 260-292 3,108,085 10/1963 Broadhead 260-22 3,242,136 3/1966 Endrey 260-47 WILLIAM H. SHORT, Primary Examiner L. L. LEE, Assistant Examiner US. Cl. X.R. 

